CN101127401A - (composite) membranes of solid polyelectrolytes bearing phosphoric acid groups and processes for their production - Google Patents

(composite) membranes of solid polyelectrolytes bearing phosphoric acid groups and processes for their production Download PDF

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CN101127401A
CN101127401A CNA2007101263837A CN200710126383A CN101127401A CN 101127401 A CN101127401 A CN 101127401A CN A2007101263837 A CNA2007101263837 A CN A2007101263837A CN 200710126383 A CN200710126383 A CN 200710126383A CN 101127401 A CN101127401 A CN 101127401A
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unsaturated monomer
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sulfonic
sheet material
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伊藤维厚
陆川政弘
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Canon Inc
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F30/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F30/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/122—Ionic conductors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
    • H01M8/1027—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having carbon, oxygen and other atoms, e.g. sulfonated polyethersulfones [S-PES]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
    • H01M8/1034—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having phosphorus, e.g. sulfonated polyphosphazenes [S-PPh]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1039—Polymeric electrolyte materials halogenated, e.g. sulfonated polyvinylidene fluorides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1058—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties
    • H01M8/106—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties characterised by the chemical composition of the porous support
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
    • H01M8/1072—Polymeric electrolyte materials characterised by the manufacturing processes by chemical reactions, e.g. insitu polymerisation or insitu crosslinking
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0088—Composites
    • H01M2300/0094—Composites in the form of layered products, e.g. coatings
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249962—Void-containing component has a continuous matrix of fibers only [e.g., porous paper, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2418—Coating or impregnation increases electrical conductivity or anti-static quality

Abstract

The invention relates to solid polyelectrolyte membranes and processes for their production. As solid polyelectrolyte materials, there have been known fluoropolymers which have perfluoroskeletons and side chains bearing sulfonic acid groups and heat-resistant resins which have hydrocarbon skeletons and contain alkylsulfonic acid or alkylphosphoric acid groups introduced thereto. The fluoropolymers are excellent in heat resistance and chemical resistance but have the problem of being expensive, while the heat-resistant resins have the problem of being poor in chemical resistance. Further, solid polyelectrolyte materials having higher electric conductivities have been desired. With the purpose of providing solid polyelectrolyte membranes having satisfactorily high electric conductivities and being excellent in heat resistance and chemical resistance and processes for producing the membranes, solid polyelectrolyte membranes are made from resins bearing both phosphoric acid groups and sulfonic acid groups which resins are obtained by copolymerizing a monomer bearing in the molecule a phosphoric acid group and an ethylenically unsaturated bond with a monomer bearing in the molecule a sulfonic acid group and an ethylenically unsaturated bond.

Description

Solid macromolecule electrolyte (compound) film and the manufacture method thereof that contain phosphate
The application of this division is based on the national applications (international application no: PCT/JP01/09209), the applying date the dividing an application for the Chinese patent application of " solid macromolecule electrolyte (compound) film and the manufacture method thereof that contain phosphate " that be October 19 calendar year 2001, denomination of invention that number is 01817703.4.
Technical field
The present invention relates to be suitable for use in the dielectric film of primary cell, secondary cell, fuel cell etc., the expression element, various transducers, signal is passed on medium, solid capacitor, (compound) film such as the solid macromolecule electrolyte of amberplex etc. and manufacture method thereof particularly relate to not with an organic solvent, thermal endurance, drug resistance and excellent size stability have solid macromolecule electrolyte (compound) film and the manufacture method thereof of high proton-conducting in wide temperature range and humidity range.
Background technology
Solid polymer electrolyte material, the promptly so-called polymer that belongs to cation exchange resin, for example report has a polystyrolsulfon acid, polyvinyl sulfonic acid, perfluorinated sulfonic acid polymer, perfluorocarboxylic acid polymer [Polymer Preprints, Japan Vol.42, No.7, pp.2490～2492 (1993), Polymer Preprints, Japan Vol.43, No.3, pp.735～736 (1994), PolymerPreprints, Japan Vol.42, No.3, pp.730 (1993)] etc.
Sulfonic solid macromolecule material is especially arranged on side chain, because with specific firm the combining of ion, perhaps has selective permeation cation or anionic character, so form granular, fibrous or membranaceous, can be used for various uses such as electrodialysis film, diffusion dialysis film, battery diaphragm.Wherein, trade mark is the sulfonic fluorine family macromolecule dielectric film of having on the side chain of perfluor skeleton of Nafion (DuPont corporate system), and thermal endurance and drug resistance are good, as the dielectric film that can use under exacting terms practicability.But, because make fluorine class dielectric film difficulty as described above, so there is the very high problem of price.
On the other hand, the solid macromolecule electrolyte that imports alkyl sulfonic acid base or alkyl phosphoric acid base in polybenzimidazoles etc. has the heat-resistant resin of hydrocarbon skeleton structure also has report (spy opens flat 9-87570 number, and the spy opens flat 9-110982 number).This solid macromolecule electrolyte is even also there is high conductivity (10 under 100 ℃ high temperature under saturation state -4～10 -2Scm -1), good thermal endurance (beginning loss of weight temperature more than 250 ℃) is arranged simultaneously, but under anhydrous state, do not have conductivity, and must use hazardous solvent such as dimethylacetylamide when making cast film (cast film).In addition because the price of heat-resistant resins such as polybenzimidazoles is very high, so consider a lot of problems are arranged as the common used materials such as fuel cell of automobile from the cost aspect.It is reported that in addition because polybenzimidazoles skeleton not only, the resistance to oxidation deterioration of the general resin with hydrocarbon skeleton is bad, so there is endurance issues (spy opens 2000-11755 number).People are looking forward to having the more solid macromolecule electrolyte of high conductivity.
Therefore the purpose of this invention is to provide and to be used for the sufficiently high conductivity of having of fuel cell, simultaneously thermal endurance and good solid polyelectrolyte membrane and the manufacture method thereof of drug resistance.
Another object of the present invention provides and can be used for the sufficiently high conductivity of having of fuel cell, simultaneously good solid polyelectrolyte membrane and the manufacture methods thereof of durability such as mechanical strength and thermal endurance, drug resistance, dimensional stability.
Summary of the invention
For waiting, the inventor that achieves the above object carried out deep research, found that the solid polyelectrolyte membrane that constitutes by the copolymer that contains sulfonic unsaturated monomer that sulfonic group more than 1 and 1 above ethene unsaturated bond are arranged in the unsaturated monomer of the phosphorous acidic group that phosphate more than 1 and 1 above ethene unsaturated bond are arranged in the molecule and the molecule, conductivity significantly improves, the temperature dependency of conductivity reduces, and thermal endurance and drug resistance are good.The inventor etc. also find the unsaturated monomer of phosphorous acidic group (perhaps contain the unsaturated monomer of phosphate and contain sulfonic unsaturated monomer) and the composition that contains polymerization initiator contained and are immersed on the stiffening piece material after the coating thereon, by polymerization, need not be with an organic solvent, in wide temperature range and humidity range high proton-conducting is arranged, can obtain the good solid macromolecule electrolyte composite membrane of mechanical strength and durability.The present invention is based on that these inventions finish.
Promptly, solid macromolecule electrolyte composite membrane of the present invention is characterized in that by being to have the sulfonic unsaturated monomer that contains of the sulfonic group that has in the unsaturated monomer of phosphorous acidic group of phosphate more than 1 and 1 above ethene unsaturated bond and the molecule more than 1 and 1 above ethene unsaturated bond to form copolymer and constitute and contain phosphate/sulfonic resin in the molecule.
The unsaturated monomer that contains phosphate is preferably used following general formula (A)
Figure A20071012638300091
Material (the R of expression 1Be hydrogen or alkyl, R 2For hydrogen or replacement or there is not the alkyl of replacement, n is 1～6 integer).R 1Be H or CH 3, R 2Be H, CH 3Perhaps CH 2Cl.
Contain sulfonic unsaturated monomer and be preferably p styrene sulfonic acid.
Manufacturing is by the method that contains the solid polyelectrolyte membrane with proton-conducting that phosphate/sulfonic resin constitutes, after it is characterized in that the mixture that contains sulfonic unsaturated monomer that will the sulfonic group that have in the unsaturated monomer of phosphorous acidic group of phosphate more than 1 and 1 above ethene unsaturated bond and the molecule more than 1 and 1 above ethene unsaturated bond be arranged in the molecule carries out curtain coating (casting), carry out copolymerization.
Preferably Photoepolymerizationinitiater initiater is added to by the unsaturated monomer of phosphorous acidic group and contain in the mixture that sulfonic unsaturated monomer forms, on the finishing die with the resulting composition curtain coating after, at least one side covers with ultraviolet permeability plate, by ultraviolet irradiation with the unsaturated monomer of phosphorous acidic group with contain sulfonic unsaturated monomer copolymerization.
First kind of solid macromolecule electrolyte composite membrane that proton-conducting is arranged of the present invention is characterized in that being made of the resin and the reinforcing sheet material of phosphorous acidic group.The unsaturated monomer that the resin that contains phosphate is preferably the phosphorous acidic group that 1 above phosphate and 1 above ethene unsaturated bond are arranged in the molecule carries out the proton-conducting solid macromolecule that polymerization forms.Reinforce sheet material and be preferably the sheet material that the fiber by inorganic substances or organic substance constitutes.The reinforcing sheet material is preferably weaves cotton cloth nonwoven fabrics, paper or resin film.Resin film is preferably little porous.
Manufacturing of the present invention is by the resin of phosphorous acidic group with the method for reinforcing first kind of solid macromolecule electrolyte composite membrane with proton-conducting that sheet material constitutes, it is characterized in that the unsaturated monomer that will the phosphorous acidic group of phosphate more than 1 and 1 above ethene unsaturated bond be arranged in the molecule contains is immersed on the stiffening piece material after the coating, will contain the polymerization of unsaturated monomers of phosphate.
In the said method preferably, the composition that includes the unsaturated monomer of phosphorous acidic group and Photoepolymerizationinitiater initiater contained be immersed on the stiffening piece material after the coating, reinforce sheet material and be clipped in the supporting substrate of ultraviolet permeability,, will contain the polymerization of unsaturated monomers of phosphate by irradiation ultraviolet radiation.
Second kind of solid macromolecule electrolyte composite membrane that proton-conducting is arranged of the present invention is characterized in that constituting by containing phosphate/sulfonic resin and reinforcing sheet material.Contain phosphate/sulfonic resin the sulfonic group that has in the unsaturated monomer of phosphorous acidic group of phosphate more than 1 and 1 above ethene unsaturated bond and the molecule more than 1 and the copolymer that contains sulfonic unsaturated monomer of 1 above ethene unsaturated bond are preferably arranged in the molecule.
Manufacturing is by the method that contains phosphate/sulfonic resin and reinforce second kind of solid macromolecule electrolyte composite membrane that proton-conducting is arranged that sheet material constitutes, it is characterized in that the composition that contains sulfonic unsaturated monomer that will the sulfonic group that have in the unsaturated monomer of phosphorous acidic group of phosphate more than 1 and 1 above ethene unsaturated bond and the molecule more than 1 and 1 above ethene unsaturated bond be arranged in the molecule contains is immersed on the stiffening piece material after the coating, the unsaturated monomer that makes phosphorous acidic group with contain sulfonic unsaturated monomer copolymerization.
In the said method, to comprise preferably that the unsaturated monomer of phosphorous acidic group, the composition that contains sulfonic unsaturated monomer and Photoepolymerizationinitiater initiater contain is immersed on the stiffening piece material after the coating, be clipped in the supporting substrate of ultraviolet permeability reinforcing sheet material, by irradiation ultraviolet radiation, will contain the unsaturated monomer of phosphate and contain sulfonic unsaturated monomer copolymerization.
First and second kind solid macromolecule electrolyte composite membrane of the present invention any 30～80 ℃ temperature range, has 10 under saturation state -5～10 -2Scm -1The high conductivity of scope, and have temperature that weight begins to reduce at excellent heat resistance such more than 200 ℃ does not cause the variation of profiles such as flexible, warp, splitting to have good dimensional stability 30～100 ℃ scopes.Especially include the solid macromolecule electrolyte composite membrane of phosphorous acidic group/sulfonic group resin, the temperature dependency of conductivity significantly reduces, and has 10 30～80 ℃ temperature ranges -3～10 -2Scm -1The high conductivity of scope.
In the conventional method when preparation proton-conducting polyelectrolyte membrane, the polyelectrolyte of preparation in advance is dissolved in the organic solvent, casting film, and manufacture method of the present invention is to carry out polymerization or copolymerization by the ultraviolet irradiation monomer composition, so avoided trouble with an organic solvent.
Description of drawings
Fig. 1 is illustrated in the side view that accompanies the part section of solid macromolecule electrolyte composite membrane state between 2 glass plates,
Fig. 2 is illustrated in the plane graph that accompanies solid macromolecule electrolyte composite membrane state between 2 glass plates,
Fig. 3 (a) is the solid macromolecule electrolyte composite membrane of embodiment 3 and 4, temperature T (℃) and conductance log (σ/Scm -1) relation curve chart,
Fig. 3 (b) is the solid macromolecule electrolyte composite membrane of embodiment 7 and 8, temperature T (℃) and conductance log (σ/Scm -1) relation curve chart,
Fig. 3 (c) is the solid macromolecule electrolyte composite membrane of embodiment 9 and 10, temperature T (℃) and conductance log (σ/Scm -1) relation curve chart,
Fig. 3 (d) is the solid macromolecule electrolyte composite membrane of embodiment 11 and 12, temperature T (℃) and conductance log (σ/Scm -1) relation curve chart,
Fig. 3 (e) is the solid macromolecule electrolyte composite membrane of embodiment 15 and comparative example 3, temperature T (℃) and conductance log (σ/Scm -1) relation curve chart,
Fig. 3 (f) is the solid macromolecule electrolyte composite membrane of embodiment 16 and comparative example 4, temperature T (℃) and conductance log (σ/Scm -1) relation curve chart,
Embodiment
Below proton-conducting solid macromolecule electrolyte (compound) film and the manufacture method thereof that includes the resin of phosphorous acidic group or contain phosphate/sulfonic resin of the present invention is elaborated.
[I] phosphorous acidic group resin and phosphorous acidic group/sulfonic group resin
The phosphorous acidic group resin that the present invention is used and phosphorous acidic group/sulfonic group resin are with following general formula (A)
Figure A20071012638300111
(R 1Be hydrogen or alkyl, R 2For hydrogen or replacement or there is not the alkyl of replacement, n is 1～6 integer) unsaturated monomer with phosphorous acidic group of expression is the material that must composition carries out polymerization or copolymerization.Preferred R 1Be H or CH 3, R 2Be H, CH 3Perhaps CH 2Cl.The above-mentioned unsaturated monomer that contains phosphate also can with other can carry out copolymerization with the unsaturated monomer that it carries out copolymerization.
(1) unsaturated monomer of phosphorous acidic group
In the unsaturated monomer that contains phosphate of general formula (A) expression, the monomer structure formula that the present invention is suitable for using is shown in table 1, and the rerum natura of these monomers is shown in table 2.These monomers are the commodity of unichemical (strain) Phosmer by name TMCommercially available product.But the unsaturated monomer of the phosphorous acidic group that the present invention can use is not limited to this.
Table 1
Figure A20071012638300131
Table 2
Trade mark (Phosmer TM) M MH CL A PE PP
Molecular weight (g)/phosphoric acid equivalent (g) 210 271 258.5 196 333 440
Proportion (20 ℃) 1.392 1.302 1.453 1.468 1.248 1.157
Index of refraction (nd at20 ℃) 1.4562 1.4815 1.4785 1.4664 1.4696 1.4577
Viscosity (poise at20 ℃) Brook field type viscometer determining (lot number) 80 (No.1) 800 (No.2) 700 (No.2) 320 (No.2) 25 (No.1) 55 (No.2)
Oxidation Theoretical value 533.3 206.6 433.3 571.4 - -
Measured value Below 500 196 Below 410 - 320 255
The pH value of product - 9.4 - - - -
Water-soluble (wt％at 20℃) 4.1 4.3 1.3 9.4 - -
(wt％at 25℃) - - 4.0 3.2
The soluble solvent of monomer Organic acid, ketone, alcohol The 2-hydroxyethyl meth acrylate, methyl alcohol, ethanol, isopropyl alcohol, acrylic acid, acetic acid Organic acid, ketone, alcohol With a left side With a left side Benzene, toluene, dimethylbenzene
Can use the unsaturated monomer of the phosphorous acidic group of general formula (A) separately, also can share more than 2 kinds.
(2) can carry out other unsaturated monomer of copolymerization
The unsaturated monomer that can carry out copolymerization with the unsaturated monomer of above-mentioned phosphorous acidic group can be divided into 2 groups following (2-1) and (2-2).
(2-1) contain the unsaturated monomer of acidic group
The unsaturated monomer that contains acidic group is the compound that has at least 1 acidic group, at least 1 ethene unsaturated bond in the molecule.Can enumerate sulfonic group, carboxylic acid group etc. as acidic group.Wherein preferably contain sulfonic unsaturated monomer, the unsaturated monomer by phosphorous acidic group and contain sulfonic unsaturated monomer copolymerization makes phosphorous acidic group/sulfonic resin.Solid macromolecule electrolyte (compound) film that includes phosphorous acidic group/sulfonic group resin not only has better conductivity, and the temperature dependency of conductivity significantly reduces.
Can enumerate allyl sulphonic acid, an allyl sulphonic acid as the example that contains sulfonic unsaturated monomer, vinyl sulfonic acid, p styrene sulfonic acid, (methyl) butyl acrylate-4-sulfonic acid, methacryloxy benzene sulfonic acid, tert-butyl group acrylamide sulfonic acid, 2-acryloyl group-2-acrylamide-2-methyl propane sulfonic acid etc.Wherein preferred p styrene sulfonic acid.But allyl sulphonic acid, an allyl sulphonic acid are because its pi-allyl causes degradative chain transfer, so use amount preferably is lower than 65 weight %.These contain sulfonic unsaturated monomer and can use separately, also can share more than 2 kinds.
As the example of the unsaturated monomer that contains the carboxylic acid group, can enumerate (methyl) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, maleic anhydride etc.These unsaturated monomers that contain the carboxylic acid group can use separately, also can share more than 2 kinds.
(2-2) do not contain the unsaturated monomer of acidic group
Except that (2-1) record, have the unsaturated monomer of the ethene unsaturated bond more than 1 to be included in this unsaturated monomer in normal temperature is not gas, molecule, what wherein be fit to is (methyl) propylene acyl cyanide, (methyl) esters of acrylic acid, replace or do not have the phenylethylene of replacement.In order to improve the drug resistance of solid macromolecule electrolyte (compound) film, preferred two (methyl) acrylic acid glycol ester that uses 1 molecule to contain a plurality of styrene unsaturated bonds, three (methyl) acrylic acid trihydroxy methyl propyl ester, two (methyl) acrylic acid hexylene glycol ester etc.
(3) weight ratio of each unsaturated monomer
Weight ratio (1)/(2) of phosphorous acidic group unsaturated monomer (1) and other unsaturated monomer (2) are preferably (1)/(2)=80/20～50/50 in 100/0～20/80 scope.In addition, in other the unsaturated monomer (2), the weight ratio that contains the unsaturated monomer (2-1) and the unsaturated monomer in addition (2-2) of acidic group, in order to control (2-1) that increases proton-conducting, scope (2-1)/(2-2)=100/0～50/50 is preferred.Therefore, especially the unsaturated monomer (2-1) that contains acidic group is when containing sulfonic unsaturated monomer, the weight ratio of phosphorous acidic group unsaturated monomer/contain sulfonic group unsaturated monomer is 100/0～20/80, be preferably 80/20～50/50, containing sulfonic group unsaturated monomer/other weight ratio that contains the acidic group unsaturated monomer is 100/0～50/50.
[II] Photoepolymerizationinitiater initiater
Photoepolymerizationinitiater initiater as joining in the monomer composition of the present invention has
(1) with R-(CO) xAdjacent many ketonic compounds class of-R ' (R, R '=hydrogen or alkyl, x=2～3) expression (for example diacetyl, dibenzyl etc.),
(2) use the alpha-carbonyl alcohols (for example benzoin etc.) of R-CO-CHOH-R ' (R, R '=hydrogen or alkyl) expression,
(3) with the acyloin ethers of R-CH (OR ")-CO-R ' (R, R ', R "=alkyl) expression (for example benzoin methylether etc.),
(4) with Ar-CR (OH)-CO-Ar (Ar=aryl, R=alkyl) expression alpha-substituted acyloin class (for example alpha-alkyl acyloin etc.) and
(5) multinuclear benzoquinones class (for example 9,10-anthraquinone etc.).
These Photoepolymerizationinitiater initiaters can use separately respectively or share.
The use amount of Photoepolymerizationinitiater initiater with respect to the total weight of unsaturated monomer, in the scope of 0.5～5 weight %, is preferably the scope of 1～3 weight %.Be lower than 0.5 weight %, in the ultraviolet irradiation time polymerization or the not end of copolymerization of regulation, the monomer of remained unreacted, not preferred.The use amount of Photoepolymerizationinitiater initiater surpasses 5 weight %, and the degree of polymerization of gained resin is low excessively, and resin has painted tendency, and is not preferred.
Among the present invention, Photoepolymerizationinitiater initiater is easy to be dissolved in the monomer mixture in order to reach, the viscosity of unsaturated monomer descends, contain easily and be immersed on the stiffening piece material, make the purposes such as thickness attenuation that reduce, make solid macromolecule electrolyte (compound) film attached to the amount on the sheet material of reinforcing, and also can add low-boiling solvents such as diluent methyl alcohol, acetone.
[III] reinforces sheet material
The reinforcing sheet material that the present invention is used is divided into 3 following classes.
(1) sheet material that constitutes by inorganic fibre
Can enumerate by weaving cotton cloth of constituting such as glass fibre, alumina fibre, asbestos fibre, slag fibre, nonwoven fabrics, paper etc.The level ground amount of the sheet material that is made of inorganic fibre is 10～60mg/cm 2, be preferably 10～40mg/cm 2, thick be 1～60 μ m, preferably in the scope of 5～40 μ m.
(2) sheet material that constitutes by organic fiber
Can enumerate by weaving cotton cloth of constituting such as nylon fiber, polyester fiber, acrylic fiber, aramid fibre, nonwoven fabrics, paper etc.But because the temperature of solid macromolecule electrolyte (compound) film rises near 100 ℃ when ultraviolet irradiation, so need it to have the enough thermal endurances that to withstand this temperature.The level ground amount of the sheet material that organic fiber constitutes is identical with the situation of (1) with thickness.But in the monomer composition of impregnation or coating, include under the situation of the unsaturated monomer that contains strong acid such as sulfonic group, by weaving cotton cloth of constituting of nylon fiber, nonwoven fabrics, paper etc. because be not suitable for a little less than the acid resistance.
(3) resin film
As impregnation or be coated with the resin film of monomer composition, films such as preferably polyethylene resin, acrylic resin, poly-3-methylpentene resin, nylon-6 resin, mylar, thermoplastic polyurethane's resin, polysulfone resin, polyethersulfone resin, polyether-ether-ketone resin, aromatic polyamide resin, pi resin, fluorine-type resin.Resin film can be that little porous film also can be a nonporous film, from the impregnation viewpoint of monomer composition consider preferred the former.But the monomer composition of impregnation comprises under the situation of the unsaturated monomer that contains strong acid such as sulfonic group, because the nylon film acid resistance is not strong, is not suitable for.
Under the situation of little porous film, the aperture of preferred microporous is as far as possible little, preferred especially sub-micron footpath.The whole percent opening of little in addition porous film is preferably big as far as possible, preferred especially 40～50% (with respect to surface areas), preferred 1～40 μ m of the thickness of resin film is more preferably in the scope of 5～25 μ m.
Reinforce the weight ratio of sheet material and monomer composition, in other words reinforce the compatibility of sheet material to monomer composition, because of the absorbability of monomer composition has a great difference, the weight ratio of generally reinforcing sheet material/monomer composition is preferably in 1/20～1/2 scope.
The manufacture method of [IV] solid macromolecule electrolyte (compound) film
By the unsaturated monomer of phosphorous acidic group with contain under the situation that sulfonic unsaturated monomer constitutes solid polyelectrolyte membrane, composition curtain coating in finishing die that will contain two kinds of unsaturated monomers and Photoepolymerizationinitiater initiater, cover with ultraviolet permeability plate, irradiation ultraviolet radiation prepares two kinds of unsaturated monomer copolymerization then.
By the unsaturated monomer of phosphorous acidic group (or the unsaturated monomer of phosphorous acidic group and contain sulfonic unsaturated monomer) with reinforce under the situation of sheet material formation solid macromolecule electrolyte composite membrane, the composition that will contain unsaturated monomer and Photoepolymerizationinitiater initiater contain be immersed on the stiffening piece material coating after, to reinforce sheet material and be clipped in the ultraviolet permeability supporting substrate, irradiation ultraviolet radiation prepares the unsaturated monomer photopolymerization.
Impregnation the reinforcing sheet material of unsaturated monomer composition when carrying out the ultraviolet irradiation polymerization, 2 supporting substrates that clip it are the ultraviolet ray transmissivity height not only, also must have the thermal endurance that heats up when ultraviolet irradiation caused polymerization, not bonding with the solid macromolecule electrolyte that the unsaturated monomer composition reaches and its polymerization obtains, good fissility is arranged.
Though normally used glass plate is very good to ultraviolet ray transmissivity and thermal endurance, but it is because bonding with the polymerization of passing through unsaturated monomer or the copolymerization gained solid macromolecule electrolyte of the present invention's use, so preferably silicon-coating ketone or fluorine class remover on the glass plate surface in advance use after perhaps sticking the thin transparent membrane of fluorine type resin.
Except that glass plate, can use perfluoroethylene thiazolinyl ether resin (PFA), poly-ethylene fluoride fork resin (PVDF) fluorine-type resin of etc.ing, can also use the good thermal endurances of ultraviolet ray transmissivity such as gathering 3-methylpentene resin, acrylic resin to reach resinous flat more than 100 ℃.
Cover with ultraviolet permeability plate behind the curtain coating unsaturated monomer composition and carry out ultraviolet irradiation, the coating that perhaps impregnation has been coated with the unsaturated monomer composition is reinforced sheet material and is clipped in when carrying out ultraviolet irradiation between 2 supporting substrates, is necessary beyond air and the unnecessary unsaturated monomer composition extrusion system.For example use when reinforcing sheet material, as shown in Figure 1, preferably between 2 supporting substrates, apply impartial pressure, remain on static state, carry out ultraviolet irradiation in the time of the maintenance level with rivet or clip.Ultraviolet irradiation intensity during photopolymerization is 5～50mW/cm 2, be preferably 10～25mW/cm 2
The thickness of solid macromolecule electrolyte (compound) film is preferably 10～100 μ m below 300 μ m, more preferably 10～30 μ m.
The present invention will be described in more detail with following embodiment, and the present invention is not limited to this.
Embodiment 1～16, comparative example 1～4
In the composition of unsaturated monomer shown in the table 3, add diluent methyl alcohol, after adjusting viscosity, with whole unsaturated monomers is 100 weight %, dissolving is as the イ Le ガ キ ユ ア 651 (2 of 2 weight % of Photoepolymerizationinitiater initiater, 2-dimethoxy-1,2-diphenylethane-1-ketone) and イ Le ガ キ ユ ア 500 (the 1-hydroxycyclohexylphenylketone+benzophenone) of 1 weight %.Adopt various nonwoven fabrics or paper as reinforcing sheet material, with the unsaturated monomer composition contain be immersed on the stiffening piece material after, as depicted in figs. 1 and 2, be coated with the reinforcing sheet material of unsaturated monomer composition that clipped impregnation between 2 glass plates of silicone remover.With high-pressure mercury-vapor lamp (Toshiba electricity material (strain) system ト ス キ ユ ア 400, HC-0411 type), official hour to impregnation shine 20mW/cm on this sheet material of reinforcing of unsaturated monomer composition 2Ultraviolet ray, make the unsaturated monomer composition carry out photopolymerization, make the solid macromolecule electrolyte composite membrane.Unsaturated monomer composition, the kind of reinforcing sheet material and the proterties of level ground amount, ultraviolet irradiation time and composite membrane are shown in table 3.
Table 3
No. Embodiment 1 Embodiment 2 Embodiment 3
Unsaturated monomer composition (wt.%) Phosmer M 50 - 50
Phosmer PP 50 95 50
PSSA (1) - - -
HDDA (2) - 5 -
Diluent MeOH (wt.%) 0 50 75 0 50 75 50 75
Reinforce sheet material Kind GF nonwoven fabrics GHN30CGL (3) GF nonwoven fabrics GHN30CGL GF nonwoven fabrics GMC050E (4)
Level ground amount (mg/cm 2) 30 30 50
Irradiation time [table+lining (sec)] 40+40 40+40 40+40
Composite membrane Resin/reinforcing sheet material (10) 9.6 7.5 4.7 8.5 6.1 4.2 7.2 4.0
Flatness Well Well Well
Pin hole Unit Do not have Do not have
Thickness (μ m) 170 140 110 160 130 110 170 120
Whether measure conductance Not Not Be Not
Table 3 (continuing)
No. Embodiment 4 Embodiment 5 Embodiment 6
Unsaturated monomer composition (wt.%) Phosmer M - 50 -
Phosmer PP 95 50 95
PSSA (1) - - -
HDDA (2) 5 - 5
Diluent MeOH (wt.%) 50 75 75 50
Reinforce sheet material Kind GF is Woven cloth GMC050E not GF Paper (5) GF Paper
Level ground amount (mg/cm 2) 50 40 40
Irradiation time [table+lining (sec)] 40+40 40+40 40+40
Composite membrane Resin/reinforcing sheet material (10) 6.0 5.0 4.5 5.3
Flatness Well Well Well
Pin hole Do not have Do not have Do not have
Thickness (μ m) 160 100 90 87
Whether measure conductance Be Not Not Not
Table 3 (continuing)
No. Embodiment 7 Embodiment 8 Embodiment 9
Unsaturated monomer composition (wt.%) Phosmer M 50 - 50
Phosmer PP 50 95 50
PSSA (1) - - -
HDDA (2) - 5 -
Diluent MeOH (wt.%) 75 50 75
Reinforce sheet material Kind PAN Paper (G) PAN Paper Aramid nonwoven fabric XL1040 (7)
Level ground amount (mg/cm 2) 38 38 40
Irradiation time [table+lining (sec)] 40+40 40+40 120+120
Composite membrane Resin/reinforcing sheet material (10) 3.8 5.0 13.3
Flatness Well Well Well
Pin hole Do not have Do not have Do not have
Thickness (μ m) 75 70 200
Whether measure conductance Be Be Be
Table 3 (continuing)
No. Embodiment 10 Embodiment 11 Embodiment 12
Unsaturated monomer composition (wt.%) Phosmer M - 50 -
Phosmer PP 95 50 95
PSSA (1) - - -
HDDA (2) 5 - 5
Diluent MeOH (wt.%) 50 75 50
Reinforce sheet material Kind Aramid nonwoven fabric XL1040 Aramid paper (8) Aramid paper
Level ground amount (mg/cm 2) 40 35 35
Irradiation time [table+lining (sec)] 120+120 120+120 120+120
Composite membrane Resin/reinforcing sheet material (10) 10.1 5.6 4.7
Flatness Well Well Well
Pin hole Do not have Do not have Do not have
Thickness (μ m) 190 45 38
Whether measure conductance Be Be Be
Table 3 (continuing)
No. Embodiment 13 Embodiment 14 Embodiment 15
Unsaturated monomer composition (wt.%) Phosmer M 50 - 50
Phosmer PP 50 95 -
PSSA (1) - - 50
HDDA (2) - 5 -
Diluent MeOH (wt.%) 50 50 70
Reinforce sheet material Kind ハイポア 6022(9) ハイポア6022 GF nonwoven fabrics GHN30CGL
Level ground amount (mg/cm 2) 25 25 30
Irradiation time [table+lining (sec)] 40+40 40+40 60+60
Composite membrane Resin/reinforcing sheet material (10) 3.1 2.7 2.3
Flatness Well Well Well
Pin hole Do not have Do not have Do not have
Thickness (μ m) 37 20 104
Whether measure conductance Not Not Be
Table 3 (continuing)
No. Embodiment 16 Comparative example 1 Comparative example 2
Unsaturated monomer composition (wt.%) PhosmerM 50 50 -
Phosmer PP - 50 95
PSSA (1) 50 - -
HDDA (2) - - 5
Diluent MeOH (wt.%) 70 50 50
Reinforce sheet material Kind Nylon wire - -
Level ground amount (mg/cm 2) 50 - -
Irradiation time [table+lining (sec)] 60+60 40+40 40+40
Composite membrane Resin/reinforcing sheet material (10) 0.8 - -
Flatness Well Well Well
Pin hole Do not have Do not have Do not have
Thickness (μ m) Approximately 100 Approximately 30 Approximately 20
Whether measure conductance Be Not Not
Table 3 (continuing)
No. Comparative example 3 Comparative example 4
Unsaturated monomer composition (wt.%) Phosmer M - -
Phosmer PP - -
PSSA (1) 100 100
HDDA (2) - -
Diluent MeOH (wt.%) 82 82
Reinforce sheet material Kind GF nonwoven fabrics GHN30CGL Nylon wire
Level ground amount (mg/cm 2) 30 50
Irradiation time [table+lining (sec)] 60+60 60+60
Composite membrane Resin/reinforcing sheet material (10) 1.4 0.3
Flatness Well Well
Pin hole Do not have Do not have
Thickness (μ m) 52 100
Whether measure conductance Be Be
Annotate: (1) PSSA: p styrene sulfonic acid
(2) HDDA: hexanediol diacrylate
(3) GF (glass fibre) nonwoven fabrics GHN-30CGL (commercially available product of Oji Paper (strain) system)
(4) GF (glass fibre) nonwoven fabrics GMC-050E (commercially available product of Oji Paper (strain) system)
(5) GF (glass fibre) paper (trial target of A Bo system paper (strain) system)
(6) PAN (polypropylene acyl cyanide) paper (trial target of A Bo system paper (strain) system)
(7) aramid nonwoven fabric XL-1040 (trial target of Japanese バ イ リ one Application (strain) system)
(8) aramid paper (trial target of A Bo system paper (strain) system)
(9) the little porous membrane Ha of PE (polyethylene) イ Port ア TM6022 (Asahi Chemical Industry's industry (strain) systems)
(10) weight ratio of resin/reinforcing sheet material
Measure the representative polyelectrolyte composite membrane of embodiment and comparative example, in the conductance of 30～80 ℃ of relative humidity 90% and temperature ranges.The result is shown in Fig. 3 (a)～(f).
Use method of the present invention as can be seen from the result of table 3 (a)～(f), can make the solid macromolecule electrolyte composite membrane that surface smoothing does not have pin hole with any reinforcing sheet material.By using diluent, can make attached to the amount of resin on the reinforcing sheet material below part.Though the thickness of the solid macromolecule electrolyte composite membrane of embodiment is in the scope of 20～200 μ m, but reinforce the ratio of adhering to of the level ground amount of sheet material, the compatibility of reinforcing sheet material and unsaturated monomer composition, resin by suitable adjustment, in other words the adhesion amount by suitable adjustment monomer composition and extrude its pressure can obtain required thickness.
From the conductance of result's solid macromolecule electrolyte composite membrane of the present invention as can be seen of Fig. 3 (a)～(f) 10 -5～10-2Scm -1, be that functional group's polyelectrolyte reaches good horizontal with the phosphate.The solid macromolecule electrolyte composite membrane that comprises phosphorous acidic group/sulfonic resin (embodiment 15 and 16) that constitutes by the copolymer of unsaturated monomer that contains phosphate and p styrene sulfonic acid particularly, the temperature dependency of conductivity significantly reduces, and has 10 30～80 ℃ temperature ranges -3～10 -2Scm -1High conductivity.Relative therewith, comparative example 3 and 4 solid macromolecule electrolyte composite membrane reduce the temperature dependency height of conductivity because use the independent polymer of p styrene sulfonic acid so compare conductivity with 16 solid macromolecule electrolyte composite membrane with embodiment 15.
Among the above embodiment, represented to have the experimental result of the solid macromolecule electrolyte composite membrane of reinforcing sheet material, the solid polyelectrolyte membrane of not reinforcing sheet material as can be seen also has identical electrolyte characteristic.Therefore do not needing to have aspect the purposes of high mechanical strength, the solid polyelectrolyte membrane of not reinforcing sheet material is fit to use.
As above narration, include phosphorous acidic group unsaturated monomer and contain the composition of sulfonic group unsaturated monomer after curtain coating, carry out copolymerization by ultraviolet irradiation etc., the composition that perhaps includes the unsaturated monomer (perhaps the unsaturated monomer of phosphorous acidic group and contain sulfonic unsaturated monomer) of phosphorous acidic group contain be immersed in be coated with on the stiffening piece material after, carry out polymerization or copolymerization by ultraviolet irradiation etc., can make solid macromolecule electrolyte (compound) film of not emitting organic solvent, having high proton-conducting at wide temperature range and humidity range.Particularly use the solid macromolecule electrolyte composite membrane of reinforcing sheet material, had the advantage of thermal endurance, resistance to chemical reagents and excellent size stability.
In addition, by the unsaturated monomer of phosphorous acidic group with contain the solid macromolecule electrolyte that includes phosphorous acidic group/sulfonic resin (compound) film that the copolymer of sulfonic unsaturated monomer constitutes, conductivity is higher, and the temperature dependency of conductivity is low.
Solid macromolecule electrolyte of the present invention (compound) film with such feature, be suitable for use as the solid electrolyte film of primary cell, secondary cell, fuel cell etc., expression element, various transducer, signal are passed on medium, solid capacitor, amberplex etc.

Claims (38)

1. solid polyelectrolyte membrane, it is made of phosphorous acidic group/sulfonic resin, it is characterized in that above-mentioned phosphorous acidic group/sulfonic resin is formed copolymer and constituted by the sulfonic unsaturated monomer that contains that sulfonic group more than 1 and 1 above ethene unsaturated bond are arranged in the unsaturated monomer of the phosphorous acidic group that phosphate more than 1 and 1 above ethene unsaturated bond are arranged in the molecule and the molecule.
2. according to the solid polyelectrolyte membrane of claim 1 record, it is characterized in that the unsaturated monomer of above-mentioned phosphorous acidic group is represented with following general formula (A),
Figure A2007101263830002C1
R in the formula 1Be hydrogen or alkyl, R 2For hydrogen or replacement or there is not the alkyl of replacement, n is 1～6 integer.
3. according to the solid polyelectrolyte membrane of claim 2 record, it is characterized in that R 1Be H or CH 3, R 2Be H, CH 3Perhaps CH 2Cl.
4. according to the solid polyelectrolyte membrane of each record of claim 1～3, it is characterized in that above-mentioned to contain sulfonic unsaturated monomer be p styrene sulfonic acid.
5. the manufacture method that the solid polyelectrolyte membrane of proton-conducting is arranged, described have the solid polyelectrolyte membrane of proton-conducting to constitute by containing phosphate/sulfonic resin, after it is characterized in that the mixture that contains sulfonic unsaturated monomer that will the sulfonic group that have in the unsaturated monomer of phosphorous acidic group of phosphate more than 1 and 1 above ethene unsaturated bond and the molecule more than 1 and 1 above ethene unsaturated bond be arranged in the molecule carries out curtain coating, copolymerization.
6. according to the manufacture method of the solid polyelectrolyte membrane of claim 5 record, it is characterized in that Photoepolymerizationinitiater initiater is added in the unsaturated monomer and the above-mentioned mixture that contains sulfonic unsaturated monomer of above-mentioned phosphorous acidic group, on the finishing die with the resulting composition curtain coating after, at least one side is with the covering of ultraviolet permeability plate, makes the unsaturated monomer of above-mentioned phosphorous acidic group and above-mentionedly contains sulfonic unsaturated monomer and carry out copolymerization by ultraviolet irradiation.
7. according to the method for claim 5 or 6 records, it is characterized in that the unsaturated monomer of above-mentioned phosphorous acidic group is represented with following general formula (A),
Figure A2007101263830003C1
R in the formula 1Be hydrogen or alkyl, R 2For hydrogen or replacement or there is not the alkyl of replacement, n is 1～6 integer.
8. according to the method for claim 7 record, it is characterized in that R 1Be H or CH 3, R 2Be H, CH 3Perhaps CH 2Cl.
9. according to the method for each record of claim 5～8, it is characterized in that above-mentioned to contain sulfonic unsaturated monomer be p styrene sulfonic acid.
10. according to the solid macromolecule electrolyte composite membrane that proton-conducting is arranged of each record of claim 1～4, it is further to comprise the composite membrane of reinforcing sheet material.
11., it is characterized in that the sheet material of above-mentioned reinforcing sheet material for constituting by inanimate matter or organic fiber according to the solid macromolecule electrolyte composite membrane of claim 10 record.
12. according to the solid macromolecule electrolyte composite membrane of claim 11 record, it is characterized in that above-mentioned reinforcing sheet material for weave cotton cloth, nonwoven fabrics or paper.
13. the solid macromolecule electrolyte composite membrane according to claim 10 record is characterized in that above-mentioned reinforcing sheet material is a resin film.
14. the solid macromolecule electrolyte composite membrane according to claim 13 record is characterized in that above-mentioned resin film is little porousness.
15. manufacture method according to the solid macromolecule electrolyte composite membrane that proton-conducting is arranged of each record of claim 5～9, described have the solid macromolecule electrolyte composite membrane of proton-conducting further to comprise the reinforcing sheet material, it is characterized in that having the composition dipping that contains the sulfonic group unsaturated monomer of 1 above sulfonic group and 1 above ethene unsaturated bond to reinforce sheet material or coating in the unsaturated monomer of the phosphorous acidic group that 1 above phosphate and 1 above ethene unsaturated bond are arranged in the molecule and the molecule, then with the above-mentioned unsaturated monomer that contains phosphate with above-mentionedly contain sulfonic unsaturated monomer copolymerization with comprising.
16. method according to claim 15 record, it is characterized in that with behind the unsaturated monomer that includes above-mentioned phosphorous acidic group, the above-mentioned composition dipping or coating that contains sulfonic unsaturated monomer and Photoepolymerizationinitiater initiater, above-mentioned reinforcing sheet material is clipped in the supporting substrate of ultraviolet permeability, by irradiation ultraviolet radiation, with the above-mentioned unsaturated monomer that contains phosphate with above-mentionedly contain sulfonic unsaturated monomer copolymerization.
17., it is characterized in that the sheet material of above-mentioned reinforcing sheet material for constituting by inanimate matter or organic fiber according to the method for claim 15 or 16 records.
18. according to the method for claim 17 record, it is characterized in that above-mentioned reinforcing sheet material for weave cotton cloth, nonwoven fabrics or paper.
19. the method according to claim 15 or 16 records is characterized in that above-mentioned reinforcing sheet material is a resin film.
20. the method according to claim 19 record is characterized in that above-mentioned resin film is little porousness.
21. have the solid macromolecule electrolyte composite membrane of proton-conducting, it is characterized in that comprising phosphorous acidic group/sulfonic resin and reinforce sheet material.
22., it is characterized in that above-mentioned phosphorous acidic group/sulfonic resin is that the sulfonic group that has in the unsaturated monomer of phosphorous acidic group of 1 above phosphate and 1 above ethene unsaturated bond and the molecule more than 1 and the copolymer that contains sulfonic unsaturated monomer of the ethene unsaturated bond more than 1 are arranged in the molecule according to the solid macromolecule electrolyte composite membrane of claim 21 record.
23. according to the solid macromolecule electrolyte composite membrane of claim 21 or 22 records, it is characterized in that the unsaturated monomer of above-mentioned phosphorous acidic group is represented with following general formula (A),
R in the formula 1Be hydrogen or alkyl, R 2For hydrogen or replacement or there is not the alkyl of replacement, n is 1～6 integer.
24. the solid macromolecule electrolyte composite membrane according to claim 23 record is characterized in that R 1Be H or CH 3, R 2Be H, CH 3Perhaps CH 2Cl.
25., it is characterized in that above-mentioned to contain sulfonic unsaturated monomer be p styrene sulfonic acid according to the solid macromolecule electrolyte composite membrane of each record of claim 21～24.
26., it is characterized in that the sheet material of above-mentioned reinforcing sheet material for constituting by inanimate matter or organic fiber according to the solid macromolecule electrolyte composite membrane of each record of claim 21～25.
27. according to the solid macromolecule electrolyte composite membrane of claim 26 record, it is characterized in that above-mentioned reinforcing sheet material for weave cotton cloth, nonwoven fabrics or paper.
28. the solid macromolecule electrolyte composite membrane according to each record of claim 21～25 is characterized in that above-mentioned reinforcing sheet material is a resin film.
29. the solid macromolecule electrolyte composite membrane according to claim 28 record is characterized in that above-mentioned resin film is little porousness.
30. the manufacture method of the solid macromolecule electrolyte composite membrane of proton-conducting is arranged, the described solid macromolecule electrolyte composite membrane that proton-conducting arranged comprises and contains phosphate/sulfonic resin and reinforce sheet material, it is characterized in that with having the sulfonic group more than 1 and the composition dipping that contains sulfonic unsaturated monomer of 1 above ethene unsaturated bond to reinforce sheet material or coating in the unsaturated monomer of the phosphorous acidic group that comprises the phosphate that has in the molecule more than 1 and 1 above ethene unsaturated bond and the molecule, make the unsaturated monomer of above-mentioned phosphorous acidic group then and above-mentionedly contain sulfonic unsaturated monomer and carry out copolymerization.
31. method according to claim 30 record, it is characterized in that to include the unsaturated monomer of above-mentioned phosphorous acidic group, behind the above-mentioned composition dipping or coating that contains sulfonic unsaturated monomer and Photoepolymerizationinitiater initiater, above-mentioned reinforcing sheet material is clipped in the supporting substrate of ultraviolet permeability, by irradiation ultraviolet radiation, with the above-mentioned unsaturated monomer that contains phosphate and above-mentionedly contain sulfonic unsaturated monomer copolymerization.
32. according to the method for claim 30 or 31 records, it is characterized in that the unsaturated monomer of above-mentioned phosphorous acidic group is represented with following general formula (A),
R in the formula 1Be hydrogen or alkyl, R 2For hydrogen or replacement or there is not the alkyl of replacement, n is 1～6 integer.
33. the method according to claim 32 record is characterized in that R 1Be H or CH 3, R 2Be H, CH 3Perhaps CH 2Cl.
34., it is characterized in that above-mentioned to contain sulfonic unsaturated monomer be p styrene sulfonic acid according to the method for each record of claim 30～33.
35., it is characterized in that the sheet material of above-mentioned reinforcing sheet material for constituting by inanimate matter or organic fiber according to the method for each record of claim 30～34.
36. according to the method for claim 35 record, it is characterized in that above-mentioned reinforcing sheet material for weave cotton cloth, nonwoven fabrics or paper.
37. according to each record of claim 30～34 to method, it is characterized in that above-mentioned reinforcing sheet material is a resin film.
38. the method according to claim 37 record is characterized in that above-mentioned resin film is little porousness.
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